Azo dyes.



UNITED STATES PATENT orrrcn.

ram. cur-ms AND ERNST Tussnn'noenn, or LUDWIGSHAFEN-ON-THE-REINE, AND LOUIS smear, or mmmmm, GERMANY, nssrenons '10 namscnn nmnm &

i SODA. FABBIK, OF ,LUDWIGSHAFEN ON-THE-RHINE, GERMANY, A. CORPORATION. v

AZO DYES.

No Drawing.

To all whom it may concern: 7 Be it known that we, PAUL JULIUS and VERNST Fossnnneenn, citizens of the Austrian Empire, residing at Ludwigshafen-on-the- Rhine, Germany, and LOUIS BLANGEY, a citizen of the Swiss Empire, residing at Mannheim, Germany, have invented new and useful Improvements in Azo Dyes, the following is a specification.

We have discovered new azo dyes which we can obtain by combining a diazo compound which is free from salt-forming groups with a derivative of 1-amino-7- naphthol possessing a constitution corresponding to the formula in which X represents an oxygen-containing group consisting of more than one atom and 'less than our atoms which may be referred to as a simple divalent acidyl group containing oxygen and R is an aromatic residue. Under the term diazo compound we include both an ordinary diazo compound, also a diazoazo compound and a tetrazo compound. Our new coloring ters can be produced as such, or on the fiber, or they can be made into. lakes. The

said new coloring matters are insoluble in water and possess excellent properties in particular, lent or very good fastness against the action of light and washing and of chlorin. They possess from red to blue shades and upon reduction with stannous chlorid, they give rise to an amin which is free from saltforming groups and also to a derivative of 1.8-diamino-7-naphthol. Those coloring matters obtainable from ortho-chlorbenzoyll-amino-7-naphthol give, on reduction with stannous chlorid, a derivative of 1. 8-diamino- 7 -na'phthol containing the residue The production of some derivatives of 1-amino-7-na hthol of the aforesaid type,

mat- I brilliant shades having excels Specification of Letters Patent. Patentgd J 11119 2'7, 1916,

Application filed July 9, 1914. Serial No. 849,873.

present invention, is described in thespecicatlon of our application Serial No. 849,872 of even date herewith.

The following examples willserve to illustrate further the nature of this invention,

which, however, isnot limited to these examples. of which Example 1: Pad cotton with a solution contammg 30 grams of ortho-chlorbenzoyl- 1-,am1no-7-naphthol, 20 cubic centimeters of 28per cent. caustic soda solution and 50 cubic centimeters of Turkey red oil in each liter and then, either directly or after drying, treat the material with a dime solution which has been prepared from 14 grams of ortho-nitranilin in each liter and to which has been added an excess of sodium acetate. The dye obtained which possesses a constitution corresponding to the formula taining the residue Example 2: Proceed as in the foregoing example 1, but using instead of the orthochlor-benzoyl-1 amino-7-naphthol, an equivalent' quantity of 2.4-dichlor-benzoyl-1- -amino-7-naphthol, and instead of the ortho- -nitranilin, nitro-anisidin A brilliant-bordeaux is obtained'which is ofexcellent fastness against the action of washing, chlorin and light.

Example 3; .Pad cotton with a solution containing- 33 grams of para-chlor-benzenesulfonyl-l-amino-7-naphthol, 20 cubic centimeters of 28 per cent. caustic soda solution and 50 cubic centimeters of Turkey red oil in each liter and then, either directly or after drying, treat the material with a diazo solution obtained from 16 grams of, chlor anisidin (OCH :NH,C1=1:2 :4)

in each liter, to which has been added an excess of sodium acetate. By this .means,

bluish=red shades of very good fastness against washing, chlorin and light are obtained.

Example 4: In the foregoing example 3,

7-naphthol of the aforesaid type can be employed.

The following table gives some of the shades obtainable from various combinations according to this invention.

- Melting point Component. de ees Diazocompoundr0m- Shade.

cent a.

Benzoyl-l-amlnofl-naphthol 208-209= Aminoazobenzene Violet-red. thohlorbenzoyl-1-amino-7-naphthol 157158 Ortho-nitranilin Turkey-red.

Do ..do Nitro-toluidin CH3:NHQ:NO2=1:4I3

Red. Nitro-anisidin OCH :NH :NO =1:2:5) Rgd with bluish 111 9. Alpha-amino-anthraquinone Red. Ni roan1s1din(0CH :NH :NOz=1:2:5) Rid with bluish I m e. .....do Bord aux.

Para-nitranilin Scarlet. Chlor-emsidln(00 Turkey-red. D0. Betaraminoenthraqujnone... Bordeaux. 2.6-Dichlorbenzoy1-1-amino-7-naphthol Ortho-nltranilin scplgpitkwth yel- 1 o s lnge.

Meta-nltro-benzoyl-l-amino-fZ-naphthol Nitro-anisldin (0CH :NH- :NO =-1:2:5). Bordeaux. Do Dlanis lqin Indi o. Para-toluene-sulfonyl-l-amino-7-naphthol Ortho-mtranilin.. Scar et. Pera-ehlor-benzene-sulfonyl-I-amino-7-naphthol... Chlor-anisid (OCH3:NH :C1=1:2:4) Bluish-red.

Now what we claim is 1. The new azo coloring matters obtain able from a diazo compound which is free from salt-forming groups and a derivative of l-amino-T-naphthol corresponding to the formula HNX-R I in Which X represents a divalent acidyl group containing oxygen, and R is an aromatic residue, which new coloring matters consist when'dry of red to blue powdersywhich are insoluble in water, and on' reduction with stannous chlorid give rise to an amin in which R represents an aromatic residue, which new coloring matters consist when dry of from red to blue powders, are insoluble in water, are free from sulfur and upon reduction with stannous chlorid give rise to an amin which is free from salt-forming groups and to a derivative of 1.8-diamino-7- naphthol containing a second carbon atom attached to the nitrogen atom of position 1.

3. The new azo coloring matter obtainable from a diazo compound which is free from saltforming groups and a derivative of 1-amino-7-naphthol corresponding to the formula HIi-COR| Y in which R, represents ahalogenated benzene residue, which new coloring matters consist when dry of from red to blue powders, are insoluble in water and free from sulfur and on reduction with stannous chlorid give rise to anamin, which is free from salt-forming groups, and to' a derivative of 1.8-diamino-7-naphthol, which contains halogen and which also contains a second carbon atom attached to the nitrogen atom of position 1.

eL'The new coloring matters obtainable from a diazo compound free from salt-forming groups and ortho-chlor-benzoyl-l-amino- 7-naphthol, which new coloring matters consist when dry of reddish powders, which are insoluble in Water, are free from sulfur, and on reduction with stannous chlorid give rise to an amin which is free from salt-forming groups, and ta e derivative of 1.8-diamino- I dry of a Turkey rcii powder, is insoluble in water, and .on reduction with. stannons 7 -naphtho1 conta ning the resldue chlorid gives rise to ortho-phenylene-diemm ..u e and to a. derivative of 1.8-diamino-7 -naph- 25 5 thol containing the residue 5. The new coloring matter obtains-bio by combining diazotizmi ortho-nitranilm 30 with ortho-chlor-benzoyl-l-emino-T-nap ossessmg 9 001% In testimony whereof we have hereun 10 thol, and p set our hands in the presence of two subsponding to the formula o 2110a I. I I @ribbg v 15 LwO PAUL JULIUS.

. e ERNST FUSSENEGGER. a LOUIS BLANGEY.

Witnesses: 20 J. Ame. Lmxn,

H. Mnnm 0001mm which new coloring matter copsits when 

